Treatment of hydrocarbons



Patented Aug 17, 1943 TREATMENT OF HYDROCARBONS Vladimir cago,

N. Ipatiefl and Vladimir Haensel, Chi- Ill.-, assignors to Universal Oil Products Company, Chicago, 111., a corporation-of Delaware No Drawing. Application August 21, 1940, Serial No. 353,509

1 Claim.

This invention relates to the use of particular catalytic materials and particular conditions of operation in reactions involving dehydrogenation of hydrocarbons, and is a continuation-in-part of our co-pending application Serial No. 274,970, filed May 22, 1939.

In one specific embodiment the present invention comprises a process for dehydrogenating hydrocarbons which comprises contacting the vapors of said hydrocarbons mixed with hydrogen in an amount of approximately -60% of the total mixture at temperatures within the approximate range of "450-700? C. and vapor space veloction with a relatively low order of accompanying ities from 200 to 10,000 with composite catalysts comprising essentially copper, zinc, and alumina,

the vapor space velocities indicated being exclusive of the hydrogen in admixture with the vapors.

In producing the preferred catalyst composite for the process of this invention, zinc of approximately -200 mesh, copper of approximately 100-120 mesh, and alumina of approximately 30-80 mesh are mixed in the desired proportions, formed into particles by pelleting, extrusion or any other suitable method, then treated with an inert gas or air with a controlled oxygen concentration at a. temperature in the approximate range of 500-600 C. In a number of runs the use of alumina of 40-50 mesh has resulted in the formation of catalyst particles of good physical structure and of relatively high catalytic activity. The proportion of the three materials indicated may be varied to produce catalysts of different activities but it has been found that the use of approximately equal parts byweight of these ingredients results in a catalyst of high activity, as measured by the dehydrogenation of butane at 000 C. using a vapor space velocity of approximately 1200. Further, we have found that cata-,

lysts with desirable hydrocarbon dehydrogenating properties result when zinc oxide replaces a portion of the alumina content of the copperzinc-alumina composites.

Particles of copper-zinc-alumina catalysts 4 prepared as indicated may be utilized as fillers in suitably heated chambers or tubes through which a gaseous hydrocarbon, as butane, may

. be passed under substantially atmospheric pressure and at a temperature in the approximate range of 400-750" C. using a vapor spacevelocity exclusive of hydrogen of the approximate order of 200 to 10,000. Liquid hydrocarbons, such as parafiins, naphthenes, or other hydro-aromatic hydrocarbons, may be dehydrogenated similarly by passage through chambers containing a dehydrogenatlng catalyst prepared according to the process of this invention. The catalyst tempera- 'ture and space velocity employed should be chos en to give the optimum degree of dehydrogenadered catalyst mixed therewith and passed through a suitable chamber operated under substantially the conditions indicated.

Dehydrogenation catalysts prepared from metal powders and a refractory support, such as alumina, according to the process of this invention do not undergo excessive carbonization during use in dehydrogenation reactions. When carbonization occurs, as after a long period of service, it-is usually advisable to burn the carbonaceous depos'its from the catalysts by treatment with a gas of controlled oxygen concentration, followed by heating in hydrogen.

The particles formed from the mixture indicated are relatively hard and resistant to breakage during use, even at high temperatures. For example, the breaking strength-of catalyst pellets formed according to the process of this invention was found to be 10 pounds in contrast with a breaking strength of 3 pounds observed on similar pellets produced from a mixture of 10% chromium trioxideand alumina.

While the catalysts comprising essentially alumina, copper, and zinc are preferred for use in the present process, it is still within the scope of the invention to substitute for the copper either inwhole or in part metals of the iron group, in-

cluding iron, nickel, and cobalt although obviously the results obtained will vary with the particular metal substituted and the extent of the substitution. j I

The following illustrative data are given to indicate typical results obtainable in the operation 1 of the process, although not with the intention of limiting the generally broad scope of the invention: a

v Example 7 v The following data were obtained using a catalyst prepared by mimng 45 parts of zinc dust, 15

following data:

V Mol. comp./ 6g 'Ii'me, a mtin. on 5 6 82 cajatlggl.

8H1 s m 6$ oleflns To Show the effect of added'hydrogen, a fresh batch of catalyst was treated with hydrogen and following this, propane gas was passed over the catalyst together with hydrogen at 550 C. The concentration. of hydrogen was approximate 38-40%, the total space velocity exclusive of hydrogen being 1200-1250. The following data was r We claim as our invention:

A process for dehydrogenating normally gaseous parafllns which comprises commingling the same with an amount of hydrogen such as to form a mixture containing about 20-60% of hydrogen, and contacting said mixture at a temperature in obtained. the approximate range of 450-700" C. with a Moles Mo]. oongmsition/IOO moles of spam space 00110 exit ges/ iH charged Time on stream, mine. g vel. vel. igg

' 02:10 totel cm 0 E Total chg. oleflns.

It should be noted'that the operating temperature is approximately 30'degrees lower using the hydrogen-propane mixture than when propane alone is processed. The olefin formation at the end of threezhours is still more than twice the amount produced in the absence of hydrogen. It.

is obvious that in the above example the total space velocity had to be kept the same.

catalyst formed by treating with air at a temperature of about 500-600 C. a mixture of approximately equal amounts of copper, zinc and alumina.

' VLADIMIR. N. IPA'I'IEFF.

VLADIMIR. HAENSEL. 

